Cyanoalkylaldoxime carbamates

ABSTRACT

D R A W I N G WHEREIN R3, R4, R5, R6, R7, R8 and n are as defined above.   WHEREIN: R1 and R2 are each selected from the group consisting of hydrogen, lower alkyl, and allyl, provided that when either R1 or R2 is hydrogen, the other substituent must be lower alkyl or allyl, and R3, R4, R5, R6, R7, and R8 are each selected from the group consisting of lower alkyl, hydrogen and phenyl, and N IS 0 OR 1. The above compounds are prepared by a variety of process routes from novel cyanoalkylaldoxime intermediates of the formula: Insecticidal and acaricidal compounds are provided having the formula:

United States Patent [72] Inventors [2i Appl. No. [22] Filed [45 1Patented 7 3 Assignee [54] CYANOALKYLALDOXIME CARBAMATES 7 Claims, NoDrawings [S2] U.S. Cl 260/465.4, 260/465 A, 260/465 D, 260/465 E,260/4651, 260/465.5, 424/304 [5 l] Int. Cl. ..-....C07c 121/30, C07cl2l/52,C07c 121/00 [50] Field oi Search 260/4654, 465 D [56] ReferencesCited UNITED STATES PATENTS 3,2l7,037 1l/1965 Payne, Jr. et al 260/453 X3,400,153 9/1968 Payne, Jr. et al 260/465.4X

Primary Examiner-Joseph P. Brust Attorney-Lawrence W. Flynn ABSTRACT:Insecticidal and acaricidal compounds are provided having the formula: MMW ver R1 wherein:

R and R are each selected from the group consisting of hydrogen, loweralkyl, and allyl, provided that when either R or R is hydrogen, theother substituent must be lower alkyl or allyl, and

R R R R R and R, are each selected from the group consisting of loweralkyl, hydrogen and phenyl, and

n is 0 or i.

The above compounds are prepared by a variety of process routes fromnovel cyanoalkylaldoxime intermediates of the formula:

wherein R R R R,,, R R, and n are as defined above.

CYANOALKYLALDOXIME CARBAMATES SUMMARY OF THE INVENTION This inventionrelates to storage stable cyanoalkylaldoxime carbamates represented bythe formula:

wherein:

R, and R are selected from the group consisting of hydrogen, loweralkyl, and allyl, provided that when either R, or R is hydrogen, theother substituent must be lower alkyl or allyl,

R R,, R,,, R R and R, are each selected from the group consisting oflower alkyl, hydrogen, and phenyl, and

n is or 1 This invention also relates to the use of the above compoundsas insecticides and acaricides.

This invention further relates to novel cyanoalkylaldoximes representedby the formula:

R R R /1\ I s I 3 NC I (|]CH=NOH B/n 6 R4 wherein R R R R R R and n areas defined above. These compounds (ll) are useful as intermediates inpreparing the insecticidal and acaricidal cyanoalkylaldoxime carbamates(I) described above. I

The term lower alkyl means straight and branched chain alkyl radicalscontaining from 1 to 3 carbon atoms; illustrative members are methyl,ethyl, n-propyl, and isopropyl.

IOR ART The following references represent the closest prior art knownto applicants:

1. U.S. Pat. No. 3,217,037

2. U.S. Pat. No. 3,400,153

3. The synthesis and Insecticidal Properties of some CholinergicTrisubstituted Acetaldehyde O-(Methyl-carbamoyl)oximes," Payne et al.,J. Agr. Food Chem, Vol. 14, No. 4, July-Aug, 1966, pgs. 356-365.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 7 Compounds The followingcompounds are illustrative of the cyanoalkylalodoxime carbamates of thisinvention (reference to com- Certain cyanoalkylaldoxime carbamates ofthis invention are characterized by a high degree of stability duringprolonged storage. For example, the compounds have shown substantiallyno decomposition after storage intervals of at least 3 months at ambientconditions of temperature and humidity.

The following compounds are illustrative of the cyanoalkylaldoximes ofthis invention (reference to compound ll).

H (l H 0 ll k 0 H 0 H 0 H 0 H 0 CH3 0 H 0 H CH3 CH3 1 H CH3 H 1 H CH3 H1 H H H 1 H H H 1 H C2H5 H 1 H CuH H 1 CH3 H 1 i Processes Thecyanoalkylaldoxime carbamates (I) of this invention wherein R1 and R2are not both lower alkyl or allyl are readily prepared by reacting anovel cyanoalkylaldoxime of the formula:

R7 R5 R3 Nolalaawm iii/n l lo 4 D wherein R3, R4, R5, R6, R7, R8, and nare as previously defined, with an isocyanate of the formula, RlNCO,wherein R1 is as previously defined in the presence of an inert solventand a catalytic amount of an organic amine (i.e., triethylamine)catalyst.

The cyanoalkylaldoximes (II) are themselves novel compounds which findutility as intermediates in the production of the insecticidal andacaricidal cyanoalkyladloxime carbamates (1) of this invention. Thestarting cyanoalkylaldoxime (ll) is prepared by the reaction of acyanoalkylaldehyde of the formula:

\t. .I' l.

with hydroxylamine wherein R3, R 4, R5, R6, R7, R8 and n are as definedabove in the presence of an inert solvent and about 1 mole of a basesuch as sodium acetate, pyridine, sodium bicarbonate, or calciumcarbonate.

(III) The required cyanoalkylaldehydes (Ill) are either readilyavailable or can be readily prepared from known starting materials inaccordance with procedures known to those skilled in the art. Thepreparation of a typical cyanoalkylaldehyde (lll) exemplified in ExampleA hereinbelow.

HHHHHHHHOOQQOQOQDO :3

The compounds of this invention wherein R1 and R2 are both lower alkylor allyl are conveniently prepared by either of two processes. In thefirst process, the cyanoalkylaldoxime (11) shown above is reacted with adi-substituted carbamoyl chloride of the formula:

Compound (V) is thereupon reacted with a mono or di-substituted amine(VI) of the formula, R l RZNH (wherein all substituents are as definedpreviously), in the presence of an inert solvent and about 1 mole of abase such as RlR2NH itself or aqueous sodium hydroxide to produce thedesired product (VII) in accordance with the following equation:

Suitable inert reaction solvents for carrying out the above reactionsinclude benzene, toluene, ethylene chloride, acetone, and t-butanol.

Reaction temperatures may range from 0 to 75 C. with a range of -50 C.preferred. The reactions may be run under superatmospheric, atmospheric,or subatrnospheric pressure with atmospheric pressures preferred.

UTILITY The cyanoalkylcarbamates of this invention are useful forcontrolling a variety of insects and acarina such as those shown inexamples 22, 23, and 24 hereinbelow. The compounds are particularlyeffective against aphids and mites. These two pest species are oftenfound in the same environment but are known to be difficult to controlwith a single chemical since the mites, in particular, build up aresistance to phosphorus-containing insecticides. The inventivecompounds are also most effective against ticks.

They are highly effective when applied to domestic animals such ascattle, pigs, and sheep which are infested with insects or acarina, andparticularly when applied to animals infested with arthropods such asticks, by the use of dipping vats, sprays, spray-races, dusts, and othermethods known to those skilled in the art.

They may be applied to the foliage of plants as dusts or liquid spraysto protect them from insects and mites which feed thereon; they may alsobe incorporated in or applied to the soil in order to protectgerminating and growing plants from soil-borne pests which attack theroot system and stems of said plants; or they may be applied to thebreeding sites of pests to control both the larvae and adult stages ofbreeding pest populations. In the latter situations the compounds may beapplied in conventional formulations such as dust, dust concentrates,granular materials, wettable powders, emulsifiable concentrates and thelike. They may be employed as an emulsion in water or other nonsolventsto which suitable surfactants, wetting agents or emulsifying agents havebeen added. They may be applied on solid carriers, such as tales andclays, as for example kaolin clay or fullers earth, or on such carriersas chalk, wood flour, silica, charcoal, activated carbon or other inertpowders. As a wettable powder, the compounds of this invention may beapplied to easily wettable carrier materials, such as attaclay with orwithout the aid of surfactants, or on less readily wettable carriers incombination with suitable surfactants.

Advantageously, the compounds of the invention may also be applied bythe most modern techniques of low-volume or ultralow-volume applicationwherein the compound is applied essentially as a technical material orin combination with a minor amount of hydrocarbon solvent such asPanasol An-S Socal 44-L Esso Han (all commercially available).

The compounds of this invention may also be applied in combination withother essentially technical materials, such as malathion, which inaddition to having insecticidal properties also serve as a formulationvehicle.

The cyanoalkylaldoximes derive their utility as intermediates in thepreparation of the useful cyanoalkylaldoxime carbamates. This utility isamply shown in examples l0 through 21 hereinbelow.

The following examples are provided to further illustrate the invention.

EXAMPLE A (PRIOR ART) Preparation of 2,2-DimethylA-cyanopentanal CH3 NCCHCHal-CH=O hi iitbr lua A stirred mixture of 7.2 g. ofisobutyraldehyde, 6.7 g. of amethylacrylonitrile, and 10.0 g. of a basicion exchange resin (Rexyn CGL in the OH fonn) was heated at about 75 C.for 6 hours. The mixture was then cooled, filtered, and concentratedunder vacuum. Distillation of the residue afforded 4.8 g. of thecolorless product, b.p. 70-73 C./0.l5 mm., n 25=l.4344.

Anal. Calc'd. for C,,H,,NO: C, 69.]; H. 9.4; N, l0.0.

Found: C, 68.4; H, 9.6; N, 9.5.

EXAMPLE 1 Preparation of 2,2-dimethyl-4-cyanobutyraldoxime A solution of32 g. of hydroxylamine hydrochloride in 45 ml. of water was added to asolution containing 44.0 g. of 2,2- dimethyl-4-cyanobutyraldehyde, b.p.82-85 C. (2.0 mm.), and 36 g. of pyridine in 450 ml. of alcohol gave amildly exothermic reaction. The solution was warmed to 45 C. to completethe reaction, concentrated to remove alcohol, diluted with water and theoxime isolated by extraction with benzene, washing and evaporation. Theoxime (37.0 g.) was obtained as a straw-colored oil which solidified atroom temperature. Analysis, calculated for C7Hl2N2O 19.99 percent N;Found 20.17 percent N.

EXAMPLE 2 Preparation of 2,2-Dimethyl-4-cyanopentanaloxime H; CH3

Following the same procedure used to prepare 2,2-dimethyl-4-cyanobutyraldoxime (i.e., example 1) but replacing2,2-dimethyl-4-cyanobutyraldehyde with 2,2-dimethyl-4- cyanopentanal (asprepared in example A) gave a 60 percent yield of crude produce, m.p.33-36 C. A sample, recrystallized from chloroform-petroleum ether atabout 60 C., gave colorless crystals, m.p. 37.039.0 C.

Anal. Calcd. for c,,H N,o=: c. 62.4; H, 9.1-, N, l8.2. Eound C, 6L3; H.9.3; N, 17.4.

EXAMPLE 3 Preparation of 2-Ethyl-2-methyl-4-cyanobutyraldoxime Followingthe same procedure used to prepare 2,2 dimethyl-4-cyanobutyraldoxime(i.e. example 1) but replacing 2,2-dimethyl-4-cyanobutyraldehyde with2-ethyl-2- methyl-4-cyanobutyraldehyde gave an 85.7 percent yield ofproduct melting below room temperature.

Anal. Culcd. for C,.H..N,o; C,62.3; H, 9.2; N, l8.2 Fgun l C, 61.5; N,17.8

Example 4 Preparation of 2-Methyl-2-Phenyl-4-CyanobutyraldoximeFollowing the procedure used to prepare 2,2-dimethyl-4-cyanobutyraldoxime (l.e. example 1 but replacing 2,2-dimethyl-4-cyanobutyraldehyde with 2-methyl-2-phenyl-4-cyanobutyraldehyde gave. from 45.0 g. of the aldehyde, 42.3 g. of theoxime as a pink oil.

Anal. Culcd. for C ,H N,O: C, 71.26; H. 6.98; N. l3.85.

Found: C. 70.8; H. 6.8; N, 13.4.

EXAMPLE 5 Preparation of 2.2-Diethyl-3 Cyanobutyraldoxime The aboveproduct was prepared following substantially the same procedure asinexample 1 except that the 2,2dimethyl- 4-cyanobutyraldehyde was replacedwith 2,2-diethyl-3- cyanobutyraldehyde.

EXAMPLE 6 Preparation of 2.3,3-trimethyi-4 -cyanopentanaloxime CH CH CHNC H- HCH=NOH The above product was prepared following substantially thesame procedure as in Example 1 except that the 2.2-dimethyl-4-cyanobutyraldehyde was replaced by 2-methyl-3,3-dimethyl-4-cyanopeutanol EXAMPLE 7 Preparation of 2,2-dimethyl-4-cyanoAphenylbutyraldoxime The above product was prepared followingsubstantially the same procedure as in example 1 except that the2,2-dimethyl- 4-cyanobutyraldehyde was replaced with 2,2-dimethyl-4-cyan0-4-phenylbutyraldehyde.

EXAMPLE 8 Preparation of 3-cyanopropionaldoxime NCCHZCHZCH NOH The aboveproduct was prepared following substantially the same procedure as inexample 1 except that the 2,2-dimethyl- 4-cyanobutyraldehyde wasreplaced with 3-cyanopropionaldehyde.

EXAMPLE 9 Preparation of 2-ethyl-3-cyanobutyraldehyde The above productwas prepared following substantially the same procedure as in example 1except that the 2,2-dimethyl- 4-cyanobutyraldehyde was replaced with2-ethyl-3-cyanobutyraldehyde.

EXAMPLE 10 Preparation of 2,Z-dimethyl-4-cyanobutyraldoxime-N-methylcarbamate CH3 0 NC CHzCHz-OH=NOHINHCH5 To a stirred mixture of37.0 g. of 2,2dimethyl-4-cyanobutyraldoxime in ml. of benzene was added17.5 g. of methyl isocyanate followed by 0.2 ml. of triethylamine. Avery mildly exothermic reaction occurred. infrared absorption spectraindicated reaction was complete in 3.5 hours at room temperature. Afterpartial concentration of the mixture under vacuum to remove anyunreacted methyl isocyanate, it was diluted with benzene and ether,washed with water and with saturated salt solution and dried withmagnesium sulfate. The carbamate was recovered by evaporation of solventand crystallized from ether to obtain 42 g. of white solid, mp. 42.5-43C.

Anul.

Found: 21.09% N EXAMPLE lll Preparation of2,Z-dimethyl-4-cyanobutyraldoxime-N.N- dimethylcarbamate CH3 CH3 To astirred mixture of 9.1 g. of 2,2-dimethyl-4-cyanobutyraldoxime and 7.4g. of potassium t-butoxide in 250 ml. of tbutyl alcohol was added 7.0 g.of dimethylcarbamoyl chloride over about a lO-minute period. Thetemperature was kept at 25-30C. by using a cooling bath. After anadditional hour most of the t-butyl alcohol was removed under vacuum andthe residue was partitioned between benzene and water. The water phasewas extracted once more with benzene and the combined organic layerswere then washed successively with small amounts of water and saturatedsalt solution. After drying the benzene mixture over magnesium sulfate,the mixture was filtered and concentrated in vacuo to give l().9 g. ofcrude crystalline product. Recrystallization from about 250 ml. of etherafforded 7.3 g. of colorless crystalline product, m.p. 73- 75 C.

Anul. Calcd. for C H,,N O,: C, 56.85; H. 8.] l; N. l9.89

Found: C. 56.85; H. 8.14; N. I995.

EXAMPLE 12 Preparation of 2.Z-dimethyl-4-cyanobutyraldoxime-N-ethylcarbamate The procedure was the same as that used for preparing theN-methylcarbamoyl derivatives (i.e. example except ethyl isocyanatereplaced methyl isocyanate. The product was obtained as a pale tan oilin 73 percent yield.

Anal. Culcd. for H N; 0,I C. 5635; H. 8.1]; N. I939. Found: C. 57.76; H.K70; N. l9.6|.

EXAMPLE l3 Preparation of 2.2-dimethyl-4-cyanobutyraldoxime-N-allylcarbamate The procedure was the same as that used for preparing theN-methylcarbamoyl derivative (i.e.. example 10 except that allylisocyanate replaced methyl isocyanate. The product was obtained in 89percent yield as a yellow oil.

Anal.

Calc'd. for C,.,H N O,: C. 59.]7 H. 7.68 N. l8.82l Found: C. 59.9]; H.8.23; N. l9l60.

EXAMPLE 14 Preparation of 2.2-dimethyl-4-cyanopentanaloxime-N-methylcarbamate The procedure was that used to prepare 2.2-dimethyl-4-cyunobutyruldoxime-N-methylcarbamute (i.e.. example 10) except lhul2.2tlimcthyl-l-cyunopcmunnltloxime (its prepared in example 2) replaced2.Z-dimcthyl-4-cyunobutyraldoxime. The yield of crude oily product waspercent. Further purification was effected by chromatography using amagnesium silicate column and eluting first with methylene chloride andthen with ether.

The procedure was that used to prepare 2,2-dimethyl-4-cyanobutyraldoxime-N-methylcarbamate (i.e. example 10) except that2-ethyl-2-methyl-4-cyanobutyraldoxime replaced2.2-dimethyl-4-cyanobutyraldoxime. The oily product, obtained in 87percent yield, showed only minor contamination by thin-layerchromatography on silica gel using 1 percent methanol in chloroform fordeveloping and iodine vapor for detection of spots.

Anal. Calc'd. for c..,H.,N.o,; C. 56.9; H. 8.1; N. 19.). Found: C. 57.8;H 8.5; N. l9.l.

EXAMPLE 16 Preparation of 2-methyl-2-phenyl-4-cyanobutyraldoxime-N-methylcarbamate The procedure was that used to prepare 2.2-dimethyl-4-cyanobutyraldoxime-N-methylcarbamate (i.e. example l0) except that2-methyl-Z-phenyl-4-cyanobutyraldoxime replaced2,2-dimethyl-4-cyanobutyraldoxime. The crude product from 35.0 g. of theoxime was chromatographed on magnesium silicate eluting with carbontetrachloride and then with methylene chloride to give 28.9 g. of purecarbamate as a viscous oil.

Anal. Calcd. for C, H,-,N,O,: C. 64.84; H. 6.6l; N. l6.2 I.

Found: C. 65.4; H,6.8; N. l5.8.

EXAMPLE 17 Preparation of 2,2-diethyl-3-cyanobutyraldoxime-N,N-methyl(allyl) carbamate The procedure was that used to prepare 2.2-dimethyl-4-cyanobutyraldoxime-N,N-dimethylcarbamate (i.e. example ll) except that2.2-diethyl-B-cyanobutyraldoxime replaced2.2-dimcthyl-4-cyunobutyraldoxime and methyl(allyl)car- The procedurewas that used to prepare 2,2-dimethyl-4- l5cyanobutyraldoxime-N,N-dimethylcarbamate (i.e. example 11) except that2,3,3-trimethyl-4-cyanopentaldoxime replaced2,2-dimethyl-4-cyanobutyraldoxime and di-isopropylcarbamoyl chloridereplaced the dimethylcarbarnoyl chloride. The oily product has theexpected carbonyl absorption at about 1,710 cm"'".

EXAMPLE 19 Preparation of 2,Z-dimethyl-4-cyano-4-phenylbutyraldoxime-The procedure was the same as that for the preparation of2,2-dimethyl-4-cyanobutyraldoxime-N-methylcarbamate (i.e. example 10)except that 2,2-dimethyl-4-cyanobutyraldoxime and ethyl isocyanatereplaced methyl isocyanate. The oily product is isolated in high yield.

EXAMPLE 20 Preparation of 3-cyanoaldoxime-N-methylcarbamate3-cyanopropionaldoxime was reacted with methyl isocyanate in the sameway as was 2,2-dimethyl-4-cyanobutyraldoxime of example 10. The product,a low melting solid,

shoyzs the expected nitrile absorption band at about 2,250 cm' EXAMPLE21 Preparation of 2-ethyl-3-cyanobutyraldoxime-N,N-

methyKethyl) carbamate The procedure was that used to prepare2,2-dimethyl-4- cyanobutyraldoxime-N,N-dimethylcarbamate (example ll)except that 2-ethyl-3-cyanobutyraldoxime replaced 2,2-dimethyl-4-cyanobutyraldoxime and methyl(ethyl)carbamoyl chloridereplaced dimethylcarbamoyl chloride. The product,

an oil, shows typical carbamate carbonyl absorption at about 1,700 cm'EXAMPLE 22 Efficacy Against Mites and Aphids The efficacy of theinventive cyanoalkylaldoxime carbamates against mites and aphids wasdemonstrated in accordance with the following test procedures.

1 Bean aphic-Aphisfabae Scopoli Compounds are tested as solutions in 65percent acetone- 35 percent water. Two-inch fiber pots, each containinga nasturtium plant two inches high and infested with about 150 aphids 2days earlier, are placed on a turntable (4r.p.m.) and sprayed for tworevolutions with a No. 154 DeVilbiss Atomizer at 20 psi. air pressure.The spray tip is held about 6 inches from the plants and the spray isdirected so as to give complete coverage of the aphids and the plants.The sprayed plants are laid on their sides on white enamel trays.Mortality counts are made after holding for one day at 70 F., and 50percent r.h.

LC-50 values are obtained in the standard manner by plotting percentmortality as a function of the compound concentration for a variety ofconcentrations. The term LC-50 means the compound concentrationexpressed in p.p.m. required to kill 50 percent of the aphids.

2. Two-spotted spider mite-Tetranychus urticae (Koch) Sieva lima beanplants with primary leaves 3 to 4 inches long are infested with about100 adult mites per leaf 4 hours before use in this test. The mite andegg infested plants are dipped for 3 seconds in the solutions used inthe above test, and the plants set in the hood to dry. They are held fortwo days at F., 60 percent r.h., and the adult mite mortality counted onone leaf under a stereoscopic microscope. The other leaf is left on theplant an additional 5 days and then examined at 10X power to estimatethe kill of eggs and of newly hatched nymphs, giving a measure ofovicidal and residual action, respectively.

Since mites are known to develop resistance to phosphoruscontaininginsecticides, the compounds were also tested against a strain ofphosphate-resistant mites as described below.

3. Phosphate-Resistant Mites The phosphate-resistant colony oftwo-spotted spider mites (Tetranychus urticae [Koch]) used weresubjected to repeated treatments with a 1:111 mixture of dimethoate,malathion and parathion periodically over a period of 9 years. LD testsshowed this colony to be approximately 50 times more resistant to thesechemicals than the susceptible colony. The inventive compounds weretested against these phosphate-resistant mites following the sameprocedure used for the susceptible mites.

Mite LC-SO values were determined in the manner described above foraphid LC-SO values.

4. Mite Systemic Tests The compound to be tested is formulated as anemulsion containing 0.1 gram of test material, 0.2 grams of Alrodyne 315emulsifier, 10 ml. of acetone and ml. of water. This is diluted ten-foldwith water to give a lOO p.p.m. emulsion for the test. A sieva lima beanplant with only the primary leaves unfolded is cut off just above soillevel and inserted into a 2- ounce bottle of p.p.m. emulsion and held inplace by a bit of cotton wrapped around the stem. The bottle is thenplaced in a ventilated box with the leaves extending outside the box,such that any possible fumes from the compound will be drawn out the endof the box rather than rising to affect the test leaves. About 50 adulttwo-spotted spider mites are placed on each leaf. After holding 3 daysat 80 F. and 60 percent r.h., mortality estimates are made.

7 Results are presented below in table I.

The high activity against aphids and mites is apparent from the data oftable I. The compounds also have systemic activity against mites.

It should be noted that although the compounds of this invention exhibitactivity against aphids comparable to well known insecticides such asparathion and dimethoate, they show greater activity than these twomaterials against susceptible mites (1.5 to 2 times greater) andremarkably greater activity 150 to 300 times) than these two compoundsagainst a strain of phosphate resistant mites. Since mites and aphidsare often found in the same environment, the activity againstphosphate-resistant mites is of particular importance since it permitscontrol of aphids and phosphate-resistant mites by application of asingle chemical.

EXAMPLE 23 Efficacy Against Insects The efficacy of the inventivecyanoalkylaldoxime carbamates against insects was demonstrated inaccordance with the following test procedures.

1. Large milkweed but-Oncopeltusfasciatus Dallas Compounds areformulated as 1 percent dusts by mixing 0.1 gram of the compound with9.9 grams of Pyrax ABB talc, wetting with 5 ml. of acetone and grindingwith a mortar and pestle until dry. Twenty-five mg. of the 1 percentdust is sprinkled evenly over the glass bottom of a seven-inch diametercage, using a screen-bottom plastic cut about five-eighths of an inch indiameter as an applicator, giving a deposit of approximately mg./sq. ft.(O.l08 mgJsq. cm.) of the 1 percent dust. Water is supplied in a 2-ouncebottle with a cotton wick, 20 adult bugs are added and a screen coverplaced on the top. Mortality counts are made after holding for 3 days at80 F. and 60 percent r.h.

2. Housefly-Musca domestica Linnaeus Groups of 25 adult femalehouseflies are lightly anesthetized with CO placed in wide-mouth pintmason jars, and covered with a screen cap. The test compound isformulated as an emulsion containing 0.1 gram of test material, 0.2 gramof Alrodyne 315 emulsifier, 10 ml. of acetone and 90 ml. of water. Twomilliliters of this emulsion are diluted to 40 ml. with 10 percent sugarsolution in a IO-gram glass vial, giving a concentration of 50 p.p.m.The mouth of the vial is covered with a single layer of cheesecloth,inverted and placed on the screen cap, so that the flies can feed on thesolution through the screen. Mortality counts are made after 2 days at80 F.

The compound of examples l0, l2, l3, l4, and killed lOO percent of themilkweed bugs while the compound of example ll killed 70 percent.

The compounds of examples 10, ll, and 14 killed 100 percent, 40 percent,and 96 percent respectively, of houseflies.

EXAMPLE 24 Efficacy Against Ticks TABLE ll Compound Prepared in ExampleNumber p.p.m.

We claim: 1. A cyanoalkylaldoxime carbamate represented by the formula:

wherein:

R, and R, are each selected from the group consisting of hydrogen, loweralkyl of C to C and allyl, provided that when either R or R, ishydrogen, the other substituent must be lower alkyl of C to C or allyl,

R R R R R and R are each selected from the group consisting of loweralkyl of C, to C hydrogen, and phenyl,andn isOor l.

2. The compound according to claim 1:

3. The compound according to claim 1:

CH3 C /CH; NC CHzCH2+CH=N-O-AJN\ CH3 CH3 4. The compound according toclaim 1:

CH3 0 H I I NCCH1CH,CCH=NO- N\ a 2H:

5. The compound according to claim 1:

l NC CH CH +-CH=NOt )-N MW mm gg V 7 CHZCH-T-CHQ 6. The compoundaccording to claim 1:

CH5 H I ll NCCHCHgCCH=N-OCN CH3 CH; CH;

7. The compound according to claim 1:

32 tl") NC CH2CH2?CH=N-O- NHC H:

2. The compound according to claim 1:
 3. The compound according to claim1:
 4. The compound according to claim 1:
 5. The compound according toclaim 1:
 6. The compound according to claim 1:
 7. The compound accordingto claim 1: